EP0170034A1 - Procédé de préparation de chloro-phényl phosphanes - Google Patents

Procédé de préparation de chloro-phényl phosphanes Download PDF

Info

Publication number: EP0170034A1
Authority: EP; European Patent Office
Prior art keywords: triphenylphosphine; reaction; chlorodiphenylphosphine; dichloride; phenyl
Prior art date: 1984-06-30
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP85107671A

Other languages

German (de)

English (en)

Other versions

EP0170034B1 (fr

Inventor

Hans-Jerg Dr. Ing. Kleiner

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Hoechst AG

Original Assignee

Hoechst AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1984-06-30

Filing date

1985-06-21

Publication date

1986-02-05

1985-06-21 Application filed by Hoechst AG filed Critical Hoechst AG

1986-02-05 Publication of EP0170034A1 publication Critical patent/EP0170034A1/fr

1988-07-27 Application granted granted Critical

1988-07-27 Publication of EP0170034B1 publication Critical patent/EP0170034B1/fr

Status Expired legal-status Critical Current

Links

YYDZNOUMWKJXMG-UHFFFAOYSA-N chloro(phenyl)phosphane Chemical class ClPC1=CC=CC=C1 YYDZNOUMWKJXMG-UHFFFAOYSA-N 0.000 title claims abstract description 8
238000004519 manufacturing process Methods 0.000 title description 3
RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 45
XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims abstract description 25
238000006243 chemical reaction Methods 0.000 claims abstract description 24
238000000034 method Methods 0.000 claims abstract description 20
125000003118 aryl group Chemical group 0.000 claims description 10
239000002253 acid Substances 0.000 claims description 5
150000007513 acids Chemical class 0.000 claims description 5
150000001805 chlorine compounds Chemical class 0.000 claims description 5
238000002360 preparation method Methods 0.000 claims description 2
QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 abstract description 16
IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 abstract description 14
IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 abstract description 11
150000001875 compounds Chemical class 0.000 abstract description 10
229920000642 polymer Polymers 0.000 abstract description 2
239000000047 product Substances 0.000 abstract description 2
239000013067 intermediate product Substances 0.000 abstract 1
239000007858 starting material Substances 0.000 description 10
XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
238000006392 deoxygenation reaction Methods 0.000 description 7
FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 7
FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 7
239000000460 chlorine Substances 0.000 description 6
-1 diphenylphosphinous acid ester Chemical class 0.000 description 6
125000001931 aliphatic group Chemical group 0.000 description 5
VGXKCBXTQFGNJF-UHFFFAOYSA-N ClP(Cl)=O.C1=CC=CC=C1 Chemical compound ClP(Cl)=O.C1=CC=CC=C1 VGXKCBXTQFGNJF-UHFFFAOYSA-N 0.000 description 4
125000001309 chloro group Chemical group Cl* 0.000 description 4
239000000203 mixture Substances 0.000 description 4
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
229910000073 phosphorus hydride Inorganic materials 0.000 description 4
239000011541 reaction mixture Substances 0.000 description 4
QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 3
238000004821 distillation Methods 0.000 description 3
OWGJXSYVHQEVHS-UHFFFAOYSA-N 1-dichlorophosphorylethane Chemical compound CCP(Cl)(Cl)=O OWGJXSYVHQEVHS-UHFFFAOYSA-N 0.000 description 2
NJLHHACGWKAWKL-UHFFFAOYSA-N ClP(Cl)=O Chemical class ClP(Cl)=O NJLHHACGWKAWKL-UHFFFAOYSA-N 0.000 description 2
QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
239000003054 catalyst Substances 0.000 description 2
230000000052 comparative effect Effects 0.000 description 2
JHNJGLVSPIMBLD-UHFFFAOYSA-N dichloro(ethyl)phosphane Chemical compound CCP(Cl)Cl JHNJGLVSPIMBLD-UHFFFAOYSA-N 0.000 description 2
LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical class ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 description 2
GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
125000000623 heterocyclic group Chemical group 0.000 description 2
SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 description 2
238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
238000010992 reflux Methods 0.000 description 2
230000007704 transition Effects 0.000 description 2
YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
239000005922 Phosphane Substances 0.000 description 1
239000004952 Polyamide Substances 0.000 description 1
241001620634 Roger Species 0.000 description 1
PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 description 1
238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
125000000217 alkyl group Chemical group 0.000 description 1
239000012298 atmosphere Substances 0.000 description 1
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
238000005660 chlorination reaction Methods 0.000 description 1
239000013065 commercial product Substances 0.000 description 1
238000001816 cooling Methods 0.000 description 1
SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
239000008240 homogeneous mixture Substances 0.000 description 1
KNQVWTDLQQGKSV-UHFFFAOYSA-O hydroxy-oxo-phenylphosphanium Chemical compound O[P+](=O)C1=CC=CC=C1 KNQVWTDLQQGKSV-UHFFFAOYSA-O 0.000 description 1
239000011261 inert gas Substances 0.000 description 1
239000000543 intermediate Substances 0.000 description 1
238000011835 investigation Methods 0.000 description 1
239000012299 nitrogen atmosphere Substances 0.000 description 1
MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
239000001301 oxygen Substances 0.000 description 1
229910052760 oxygen Inorganic materials 0.000 description 1
229910000064 phosphane Inorganic materials 0.000 description 1
239000004476 plant protection product Substances 0.000 description 1
229920002647 polyamide Polymers 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
239000002904 solvent Substances 0.000 description 1
239000003381 stabilizer Substances 0.000 description 1
150000004763 sulfides Chemical class 0.000 description 1
TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)

Definitions

Plant protection products are obtained, for example - starting from dichlorophenylphosphine - via the phenylthiophosphonic dichloride C 6 H S P (S) C1 2 .
dichlorophenylphosphine benzenephosphonous acid C 6 H 5 P (O) (OH) H is also known in a known manner, which, by itself or in the form of its salts, is of considerable economic importance as a stabilizer for polyamides.
chlorophenylphosphines A number of different methods are known for producing the chlorophenylphosphines. For example, according to the process described in DE-A-3 216 381, chlorodiphenylphosphine and dichlorophenylphosphine are obtained by reacting triphenylphosphine (C 6 H 5 ) 3 P with phosphorus trichloride PC1 3 at temperatures between about 320 and 700 ° C obtained without the addition of any catalysts; the implementation follows the following equation:
triphenylphosphine also converts with dichlorophenylphosphine to chlorodiphenylphosphine (DE-A-3 216 379):
Aliphatic chlorophosphanes can also be obtained, inter alia, by deoxygenation of the chlorides of aliphatic P-0 acids.
R 2 aliphatic radical are aromatic (or heterocyclic) aliphatic phosphinic acid chlorides
R 2 Cl around aromatic (or heterocyclic) phosphonic acid dichlorides.
diphenylphosphinoyl chloride (C 6 H 5 ) 2 P (O) Cl can be deoxygenated by means of triphenylphosphine to chlorodiphenylphosphine; the chloro-diphenylphosphine can then in turn be used again to deoxygenate the dichloride of benzenephosphonic acid to dichlorophenylphosphine.
the yields of the two individual reactions a) and b) are all between about 80 and 100% of theory
the success and the high yield deoxygenation of the chlorides of purely aromatic P-0 acids (diphenylphosphinoyl chloride, benzenephosphonic dichloride) using an aromatic phosphine (triphenylphosphine, chlorodiphenylphosphine) were surprising because purely aliphatic phosphonic acid dichlorides with the (aromatic) triphenyl deoxygenate only very incompletely to the corresponding dichlorophosphanes.
the starting materials of the individual reaction b) (benzenephosphonic dichloride and chloro-diphenylphosphane) fall purely formally also under the general formulas of the starting materials for the process according to DE-A-32 44 031;
the C6H5-Cl exchange reaction typical of the process of the aforementioned DE-A in the case of heating benzenephosphonic dichloride with chlorodiphenylphosphine takes place only to an extraordinarily minor extent.
the reaction that takes place practically exclusively here is the deoxygenation of benzene phosphonic acid dichloride.
the starting compounds for the process according to the invention are diphenylphosphinoyl chloride and triphenylphosphine or benzenephosphonic dichloride and chlorodiphenylphosphine.
Diphenylphosphinic acid chloride is obtained, for example, by alkaline hydrolysis of triphenylphosphine oxide and subsequent chlorination, for example using SOC1 2 .
Triphenylphosphine is a common commercial product, the production of which hardly needs to be reported.
Benzene phosphonic acid dichloride is easily obtainable, for example, by reacting bromobenzene with triethyl phosphite / Ni catalyst with subsequent action by COC1 2 or SOC1 2 .
Chlorodiphenylphosphine is accessible by deoxygenation of diphenylphosphinoyl chloride according to individual reaction a) of the process according to the invention or, if appropriate, also by the methods of the prior art mentioned at the beginning.
the starting compounds diphenylphosphinoyl chloride and triphenylphosphine or benzenephosphonic dichloride and chlorodiphenylphosphine are first mixed.
diphenylphosphinic acid chloride and triphenylphosphine homogeneous mixtures may only be obtained at higher temperatures.
the components are advantageously used in a molar ratio of about 1: 1. However, excesses of one or the other component are possible.
the mixture of the starting materials is preferably reacted under excess pressure, in particular under the (autogenous) pressure which arises in a closed reaction vessel.
the response time here is between about one and thirty hours.
the mixture of starting materials is preferably reacted at normal pressure.
the mixture of the starting materials is expediently metered into a heated reaction zone with the aid of a metering device.
a suitable reaction zone is e.g. an electrically heated pipe.
the reaction mixture emerging from the reaction zone is collected in a receiver. It can be advantageous to cool.
the response times here are practically of the order of seconds or minutes.
the process can be carried out continuously or batchwise.
reaction mixtures are worked up in a conventional manner, e.g. with the help of distillation processes.
triphenylphosphine oxide When triphenylphosphine oxide is obtained, its tendency to crystallize can also be used to crystallize off the main amount of triphenylphosphane oxide (if appropriate using a suitable solvent).
the invention represents a considerable enrichment of the technology.
the distillate consisted of 30.9% dichlorophenylphosphine, 28.9% chlorodiphenylphosphine, 31.8% diphenylphosphinoyl chloride, 3.8% unreacted benzenephosphonic dichloride, 1.5 based on a 31 P NMR spectrum % Triphenylphosphine oxide and 3.1% triphenylphosphine.
the individual components given can be separated by distillation, 30.9% of 55 g give about 17 g of dichlorophenylphosphine. Without taking into account the benzene phosphonic acid dichloride to be recovered, this gives a yield of approx. 93% of theory, based on the benzene phosphonic acid dichloride used.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Health & Medical Sciences (AREA)
Life Sciences & Earth Sciences (AREA)
Biochemistry (AREA)
General Health & Medical Sciences (AREA)
Molecular Biology (AREA)

EP85107671A 1984-06-30 1985-06-21 Procédé de préparation de chloro-phényl phosphanes Expired EP0170034B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE19843424182 DE3424182A1 (de)	1984-06-30	1984-06-30	Verfahren zur herstellung von chlor-phenyl-phosphanen
DE3424182		1984-06-30

Publications (2)

Publication Number	Publication Date
EP0170034A1 true EP0170034A1 (fr)	1986-02-05
EP0170034B1 EP0170034B1 (fr)	1988-07-27

Family

ID=6239553

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP85107671A Expired EP0170034B1 (fr)	1984-06-30	1985-06-21	Procédé de préparation de chloro-phényl phosphanes

Country Status (4)

Country	Link
US (1)	US4708824A (fr)
EP (1)	EP0170034B1 (fr)
JP (1)	JPS6118794A (fr)
DE (2)	DE3424182A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4990674A (en) *	1989-06-14	1991-02-05	Occidental Chemical Corporation	Synthesis of aliphatic aromatic phosphine oxides
CN107936056B (zh) *	2017-12-21	2019-07-16	河南省科学院化学研究所有限公司	一种二芳基磷溴化合物的制备方法
CN107936057B (zh) *	2017-12-21	2019-07-16	河南省科学院化学研究所有限公司	一种二芳基磷氯化合物的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
SU362026A1 (ru) *	1970-04-24	1972-12-13		Способ получения метилдихлорфосфина
EP0110305A1 (fr) *	1982-11-27	1984-06-13	Hoechst Aktiengesellschaft	Procédé de préparation de composés phosphore-chlore aromatiques
EP0122587A2 (fr) *	1983-04-16	1984-10-24	Hoechst Aktiengesellschaft	Procédé de préparation de chlorophosphanes organiques

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3024278A (en) *	1959-10-01	1962-03-06	Monsanto Chemicals	Chemical process
US3094559A (en) *	1960-05-05	1963-06-18	Stauffer Chemical Co	Method for the preparation of diphenylphosphinous chloride
US3579576A (en) *	1964-02-25	1971-05-18	Sun Oil Co	Organophosphorus compounds and a process for the making thereof
BE791257A (fr) *	1971-11-10	1973-05-10	Poudres & Explosifs Ste Nale	Procede de preparation d'oxydes et de sulfures de phosphines etnouveauxsulfures de phosphines
DE2965566D1 (en) *	1978-07-14	1983-07-07	Basf Ag	Acylphosphinoxide compounds, their preparation and their use
DE3216381A1 (de) *	1982-05-03	1983-11-03	Hoechst Ag, 6230 Frankfurt	Verfahren zur herstellung von chlor-phenyl-phosphanen
DE3216379A1 (de) *	1982-05-03	1983-11-03	Hoechst Ag, 6230 Frankfurt	Verfahren zur herstellung von chlor-diphenyl-phosphan
DE3216380A1 (de) *	1982-05-03	1983-11-03	Hoechst Ag, 6230 Frankfurt	Verfahren zur herstellung von dichlor-phenyl-phosphan

1984
- 1984-06-30 DE DE19843424182 patent/DE3424182A1/de not_active Withdrawn
1985
- 1985-06-21 EP EP85107671A patent/EP0170034B1/fr not_active Expired
- 1985-06-21 DE DE8585107671T patent/DE3563969D1/de not_active Expired
- 1985-06-28 US US06/750,030 patent/US4708824A/en not_active Expired - Fee Related
- 1985-06-28 JP JP60140671A patent/JPS6118794A/ja active Pending

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
SU362026A1 (ru) *	1970-04-24	1972-12-13		Способ получения метилдихлорфосфина
EP0110305A1 (fr) *	1982-11-27	1984-06-13	Hoechst Aktiengesellschaft	Procédé de préparation de composés phosphore-chlore aromatiques
EP0122587A2 (fr) *	1983-04-16	1984-10-24	Hoechst Aktiengesellschaft	Procédé de préparation de chlorophosphanes organiques

Also Published As

Publication number	Publication date
EP0170034B1 (fr)	1988-07-27
US4708824A (en)	1987-11-24
DE3563969D1 (en)	1988-09-01
JPS6118794A (ja)	1986-01-27
DE3424182A1 (de)	1986-01-09

Legal Events

Date	Code	Title	Description
1985-12-07	PUAI	Public reference made under article 153(3) epc to a published international application that has entered the european phase	Free format text: ORIGINAL CODE: 0009012
1986-02-05	AK	Designated contracting states	Designated state(s): CH DE FR GB IT LI NL
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1987-08-05	17Q	First examination report despatched	Effective date: 19870619
1988-06-11	GRAA	(expected) grant	Free format text: ORIGINAL CODE: 0009210
1988-07-27	AK	Designated contracting states	Kind code of ref document: B1 Designated state(s): CH DE FR GB IT LI NL
1988-09-01	REF	Corresponds to:	Ref document number: 3563969 Country of ref document: DE Date of ref document: 19880901
1988-09-08	ITF	It: translation for a ep patent filed
1988-10-26	GBT	Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
1988-11-10	ET	Fr: translation filed
1989-06-08	PLBE	No opposition filed within time limit	Free format text: ORIGINAL CODE: 0009261
1989-06-08	STAA	Information on the status of an ep patent application or granted ep patent	Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT
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1989-08-16	PGFP	Annual fee paid to national office [announced via postgrant information from national office to epo]	Ref country code: DE Payment date: 19890816 Year of fee payment: 5
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